Method of making ceramic dielectric material



METHOD OF MAKING CERAMIC DIELECTRIC MATERIAL ilohn M. Herbert, Horton, England, assignor to The Plessey Company Limited, Ilford, England, a British company No Drawing. Application 51115 23, 1956 Serial No. 599,662

1 Claim. 161. 106- 39) from a mass of semi-conducting particles separated from each other by insulating barriers.

The application of these methods of enhancing the dielectric constant of barium titanate has not been practieable up to now. Normally barium titanate must be fired in air to a temperature between 1250 and 1450 C. to give an-insulating, dense ceramic. Under these conditions all base metals are oxidised and in the oxidised state react with barium titanate to form substantially insulating material's. Palladium and platinum remain metallic but their 2,934,442 resented Apr. 2e, 1 9eo ICC 2 The above described dielectric material (or the p'r'e' cursors therefor) is used in'theprocesso'f the present invention. v 1

In this specification the phrase ceramic dielectric ma terial of the kind specified" is usedto designatetheceramic dielectric material described in my co-pending US.

patent applications Ser. Nos. 542,478 and 582.945.

According to the present invention there is provided process for thev production of a ceramic dielectricmjaterial which comprises the steps of a firing in air for 2'lio'1ifs at 1100 C. a mixture of 130 :parts by weight of barium carbonate, 52.6 vparts by weight of titanium dioxide and l 9.parts byweight of mangano'us carbonate tdprodrice a sinter'ed in't'ei ilitised mixture o'f 'the constituentmate rials, '(b) grinding tlie'si-iitered mixture to 'aparticle size of l to 10 microns, (c) mixing isparts by Weight of the ground sintered mixture with 3 parts by weight of car'- bonyl iron powder 'having a particle size of 3 to 8"rn i c'rons, (0.) adding a binder to the mixture of the carbonyl iro'n powder and ground sintered mixture and compacting the composition obtained to the'de'si'red shape, and a firing'tlie same'in'hydrogen'to 120D C.,'the firing being effected in about .four hours from room temperature.

The substancewliich is a conductor or yields a conduc to'r on firing inhyd'rogen may be a metal or a met'allic compound, egg. an oxide, reducibleto the metal by in a reducing atmosphere. Alternatively it may bea cost prevents their large scale use. Silver and gold melt i i i V prisinga dispersion of discreteparticles of a conduct ve oxidising the'exterior of these particles and simultaneously in some way'cementing-them together with oxidised (and, therefore, insulating) barium titanate to make an artificial dielectric; but such a'proc'ess has been fo'und very difiicult to control in practice.

, In my ctr-pending US. application Ser. No. 542,478, filed September 13," 1955, there is described a'dielec tric material which consists essentially of BaTiO and MnO in quantities corresponding to the formula 2BaTiO .MnO. This dielectric material is produced by firing a mixture of BaCO TiO and MnO in powder form to produce a sintered dielectric material having a composition corresponding to the above stated formula 2BaTiO .MnO. The material contains free manganous oxide and a compound closely resembling barium titanate and which is believed to be a solution of manganous oxide in barium titanate. When the above prepared dielectric material is fired in a reducing atmosphere, such as hydrogen, an insulating body is obtained which has a high dielectric constant.

In my co-pending U.S. application No. 582,945, filed May 7, 1956, it is further explained that the BaTiO, and MnO can be in such proportions as to correspond to the formula 4BaTiO .MnO or 6BaTiO .MnO as alternatives to the proportions specified in co-pending US. application No. 542,478. My co-pending U.S. specification Ser. No. 582,945 also indicates that it is possible to substitute other elements for up to 50 mol percent of the barium and titanium. It is stated that substitutions of more than a few percent result in a material of reduced permittivity but it may have a lower temperature coefiicient of permittivity. Elements which may be substituted for barium are magnesium, beryllium, calcium, strontium, yttrium and lanthanum. For titanium there may be substituted zirconium, hafnium, cerium, thorium, tin and tantalum. Magnesium may be used in part instead of manganese, substitution of up to 75 mol percent being possible without appreciably alfecting the dielectric properties.

barium titanate, n'iodified oriunmodified by a'ddition's, which become's'c'onductive on firing in a reducing atmosphere, or percursors for such a form or barium titanate.

The invention thusfaffords a dielectric material eqm;

material in an insulating medium consisting of a ceramic dielect'ric m'aterial of the kind specified. I V i The following examples 'aregiven by wayof illustration and without limitation. .-Examp'le 1 From 5 to 25, parts by weight of ferric oxide'aremixed with from 95 to parts of a'ba'rium titanate of the kind specified (or it s precursors) which yields an insulator on 'firi'ng'for two hours 'in hydrogen, and area from 6 to 16 hours to 1100 C. in air to give a sintered, interdifr'used mixture of the constituent oxides. This mixture is then ground to a particle size of 1 to IOmici-ons and pressed or moulded under a moulding pressure of 5 tons per square inch to the required shape of dielectric. It is then fired in hydrogen to 1200 C. for 1 hour when it sinters to a ceramic material containing iron particles which are in the form of a finely divided dispersion. The cooling from 1200 C. is in two stages, the first taking between 10 and 30 minutes to cool from 1200 C. to 1000 C., and the second stage taking 12 hours to cool from 1000 C. to 20 C. An electrode material, for example iron oxide, can be applied to suitable areas of the body before firing, in which case a substantially complete condenser is obtained in one furnacing operation, or silver may be evaporated on to the fired body to form electrodes in the required area.

Example 2 A form of barium titanate of the kind specified which will fire in hydrogen to form an insulator is mixed with an unmodified form which will fire in hydrogen to form a conductor and the mixture is fired in hydrogen. In this case the mixture that is eventually to be conducting is fired to 1300 C. in hydrogen for 2 hours. The sintered, partially reduced product is ground to relatively coarse particles and sieved through a 200 mesh screen; the fraction passing through is rejected. The coarse particles are such that by weight of the powdered material should pass through a I.M.M. screen and all through a 30 LMZM. screen. 50 to 80 parts of this said product are mixed with 50 to 20 parts of a non-reducing composition comprising a barium titanate modified by the addition of manganese oxide whichhas asmaller particle size, all less than microns, and the mixture is fired in hydrogen to 1200 C. for 1 hour. The cooling of the fired mixture is effected-in twostages, the first taking between and 30 minutes to cool from 1200 C. to 1000 C. and the second taking between 4 and 12 hours-to cool from 1000 C.'- to C. The density of the resulting ceramic is 5.5 to.5.8 gr ams per cubic centimetres, The moulding pressure is fiveto'ns per square inch. As before, electrodes can be, applied before or after final furnacing.

made byfiring, together 130 parts by weight of'barium carbonate, 526 parts of titanium dioxide and 19 parts of manganese carbonate. The barium carbonate and manganese carbonate are precipitated materials dried at low temperatures with particlesizes "ranging mainly between 0.5 andS i. The titanium dioxide is a pigment powder of particle size mainly 0.1 tol and with the anatase crystal structure. The materials mustbe well mixed and should be fired for 2 hours at 1100 C. in air. After firing the material is ground to a particle size of "1 to 10 microns and 15 parts by weight are mixed with 3 parts by weight of carbonyl iron powder having a particle size of 3 to 8 microns. A binder is added to the mixture which is then compacted at-10 tons per square inch into the form of a pellet or otherwise formed into a desired shape. A

suitable binder comprises. a 30% solution of polybutyl-. methacrylate in acetone. J The shapes obtained are fired and the shapes having a density of 5.8 to 6.0 grammes per square centimetre and being constituted by metallic iron in barium manganese titanate. The carbon formed from A ceramic dielectric material of the kindspecified 1s said shapes by evaporating silver in a vacuum on to suitable areas.

The effect of the metal content is to increase the dielectric constant relative to that of the dielectric in the absence of metal by a factor lying between 1.5 and 6. The resistivity is reduced by the same factor whilst the power factor is unafiected. In the case of Example 1, materials containing 9.6 and 11.2 percent by volume of metal content gave permittivities at room temperature of 3630 and 9800 with'power factors of 2 and 4.5 percent. The resistivities being 3 10 and 1X 10 ohms per centimetre respectively. The results obtainable in the case of Examples 2 and 3 are similar.

While condensers suitable for any electrical purpose may be prepared from'the dielectric material of the invention, it is particularly adapted for types usuable in the suppression of electromagnetic radiation from machinery or devices which produce electric sparks during their normal operation.

What is claimed is: e v v A process for the production of a ceramic dielectric material which comprises the steps of (a) firing in air for 2 hours at 1100 C. a mixture of parts by weight of barium carbonate, 52.6 parts by weight of titanium dioxide and 19 parts by weight of ,manganous carbonate to produce asintered inter-difiused mixture of the constituent materials, ([2) grinding the sintered mixture to a particle size of 1 to 10 microns, (c) mixing 15 parts by weight of the ground sintered mixture with 3 parts by weight of carbonyl iron powder having a particle size of 3 to 8 microns, (d) addin g a binder to the mixture of the carbonyl iron powder and ground sintered mixture and compacting the composition obtained to the desired shape, and (e) firing the same in hydrogen to 1200 C., the firing being effected in about four hours from room temperature.

References Cited in the file of this patent I UNITED STATES PATENTS 2,529,719 Wentworth Nov. 14, 1950 2,695,240 Oshry Nov. 23, 1954 2,750,657 7 Herbert et a1. June 19, 1956 V FOREIGN PATENTS 460,764 Canada Nov. 1, 1949 

